EP2931406B1 - One-pot method for the synthesis of cu-ssz-13 - Google Patents

One-pot method for the synthesis of cu-ssz-13 Download PDF

Info

Publication number
EP2931406B1
EP2931406B1 EP13801583.9A EP13801583A EP2931406B1 EP 2931406 B1 EP2931406 B1 EP 2931406B1 EP 13801583 A EP13801583 A EP 13801583A EP 2931406 B1 EP2931406 B1 EP 2931406B1
Authority
EP
European Patent Office
Prior art keywords
range
ssz
polyamine
anyone
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13801583.9A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2931406A1 (en
Inventor
Manuel Moliner MARIN
Raquel Martínez FRANCO
Avelino Corma CANÓS
Joakim Reimer THØGERSEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore AG and Co KG
Original Assignee
Umicore AG and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Priority to PL13801583T priority Critical patent/PL2931406T3/pl
Publication of EP2931406A1 publication Critical patent/EP2931406A1/en
Application granted granted Critical
Publication of EP2931406B1 publication Critical patent/EP2931406B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper

Definitions

  • the present invention relates to a method for the direct preparation of SSZ-13 zeolite containing copper atoms.
  • This new method requires the specific combination of a copper polyamine complex and an additional organic molecule, which acts as organic structure directing agent (OSDA).
  • OSDA organic structure directing agent
  • Cu-SSZ-13 materials synthesized following the present methodology may be used as catalysts for the selective catalytic reduction (SCR) of NOx.
  • zeolites can be classified depending on the size of their pores, whose ring openings are delimited by a number of T atoms. In this sense, small pore zeolites show openings with 8-T atoms, medium pore zeolites present openings with 10-T atoms, large pore zeolites have openings with 12-T atoms, and finally, extra-large pore zeolites present openings with more than 12-T atoms.
  • zeolite with specific physico-chemical properties for a particular chemical process will directly depend on the nature of reactants and products involved in the process (such as size, shape, hydrophobicity, etc.), and also on the reaction conditions.
  • reactants and products such as size, shape, hydrophobicity, etc.
  • the nature of the reactants and products will affect to the diffusion of those molecules within the pores and cavities of the zeolite, and consequently, the selection of the zeolite with the adequate pore topology for the chemicals involved in the reaction will be essential.
  • the zeolite must be stable, both structurally and chemically, on the required reaction conditions.
  • NOx nitrogen oxides
  • SCR selective catalytic reduction
  • CHA structure has received much attention.
  • This material is formed by a three-directional small pore system (8-T atoms) containing large cavities with D6R cages in its framework.
  • Cu-substituted small pore zeolites perform as excellent catalysts in the SCR of NOx with ammonia or hydrocarbons in the presence of oxygen.
  • the conventional metal-containing zeolite (Me-zeolite) form is achieved by post-synthetic metal ion-exchange procedures. In this sense, several steps are required for achieving the Me-zeolite such as hydrothermal synthesis of the silicoaluminate, calcination to remove the OSDA, transformation to NH 4 -form if required, metal ion exchange, and finally, calcination to obtain the final Me-zeolite. All these steps contribute to increase the overall cost of the material.
  • the method reported by BASF researchers to prepare the one-pot synthesis of Cu-SSZ-13 always requires the specific combination of two organic ammonium cations (such as N,N,N-trimethyl-1-adamantammonium and benzyl trimethylammonium, N,N,N-trimethyl-1-adamantammonium and tetramethylammonium, or benzyl trimethylammonium and tetramethylammonium), and the addition of an organometallic complex formed by reacting ammonia with a copper salt.
  • two organic ammonium cations such as N,N,N-trimethyl-1-adamantammonium and benzyl trimethylammonium, N,N,N-trimethyl-1-adamantammonium and tetramethylammonium, or benzyl trimethylammonium and tetramethylammonium
  • the improved process involves a simple combination of a copper-polyamine complex with an additional and unique organic molecule acting as OSDA capable to template the SSZ-13 zeolite. Following this simple combination of a Cu-complex with the additional organic molecule is possible to direct the "one-pot" synthesis of Cu-SSZ-13 under broad Si/Al ratios and controlled Cu contents in the final zeolite.
  • This new method clearly improves the physico-chemical properties of the Cu-SSZ-13 materials achieved following the Xiao's procedure [ Chem. Commun, 2011, 47, 9783 ; Chin. J. Catal. 2012, 33, 92 ], and on the other hand, simplifies the preparation method reported by BASF researchers since only a single OSDA is required, and moreover, the use of ammonia is avoided.
  • the invention provides a process for the direct synthesis of Cu-SSZ-13 comprising the following steps:
  • Cu-TEPA a Cu-complex
  • an additional organic molecule capable to direct SSZ-13 zeolite such as N,N,N-trimethyl-1-adamantammonium or benzyl trimethylammonium
  • these Cu-complex molecules remain intact within the as-prepared SSZ-13 crystals after crystallization as revealed by UV-Vis spectroscopy (see Figure 2 ) yielding active extra-framework copper cationic species after calcination.
  • step (i) of the inventive process all possible silicon, aluminum and copper sources may be employed in the preparation of Cu-SSZ-13.
  • any polyamine or mixtures of different polyamine molecules capable of forming a complex structure with Cu atoms can be used, these include primary, secondary or tertiary amines.
  • Preferred polyamines are tetraethylenepentamine, triethylenetetramine, 1,4,8,11-tetraazacyclotetradecane and 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane.
  • the final synthesis mixture in step (i) comprises preferably the following molar compositions: SiO 2 : a Al 2 O 3 : b Cu : c Polyamine : d OSDA : e H 2 O : f Alk : g F, wherein
  • the crystallization step (ii) in the inventive process is performed by hydrothermal treatment in an autoclave, under static or dynamic conditions.
  • the preferred temperature is ranged from 100 to 200°C, more preferably in the range of 130 to 175°C.
  • the preferred crystallization time is ranged from 6 hours to 50 days, more preferably in the range of 1 to 20 days and more preferably in the range of 2 to 15 days. It should be taken into consideration that the components of the synthesis mixture may come from different sources, and depending on them, times and crystallization conditions may vary.
  • crystals of SSZ-13 can be added as seeds in quantities up to 25% by weight respect to the total of oxides to the synthesis mixture. These can be added before or during the crystallization of Cu-SSZ-13.
  • Cu-SSZ-13 crystals are separated from the mother liquor.
  • the solids can be washed and separated from the mother liquor by decantation, filtration, ultrafiltration, centrifugation, or any other solid-liquid separation technique.
  • the process of the present invention can further comprise a stage of elimination of the organic occluded inside the material, when the aim is to produce the calcined crystalline material. This can be performed by extraction and/or thermal treatment at temperatures over 25°C during a period of time between 2 minutes and 25 hours.
  • the material produced by the invention may be pelletized in accordance with known techniques. They can also be used in different processes.
  • the SCR of NOx wherein the molecular sieve prepared according to the present invention is used as catalyst in presence of a reductant, as ammonia, urea and/or hydrocarbon, is illustrated in the examples below.
  • the catalytic activity in of the molecular sieve catalyst is summarized in Table 3 below.
  • a 20%wt aqueous solution of copper (II) sulfate (98%wt, Alfa) was mixed with 36 mg of tetraethylenepentamine (TEPA, 99%wt, Aldrich), and kept under stirring during 2 hours.
  • TEPA tetraethylenepentamine
  • 1041 mg of an aqueous solution of N,N,N-trimethyl-1-adamantammonium hydroxide (TMaDA, 16%wt) were added and maintained under stirring during 15 minutes.
  • the gel was transferred to an autoclave with a Teflon liner, and heated to a temperature of 150°C during 14 days under static conditions.
  • the sample after hydrothermal crystallization was filtered and washed with abundant distilled water, and finally dried at 100°C.
  • the solid was characterized by Powder X-ray Diffraction (PXRD) obtaining the characteristic PXRD pattern of the SSZ-13 material (see Cu-SSZ13-1 in Figure 1 ).
  • the chemical analysis of the resultant solid indicates a Si/Al and Cu/(Si+Al) ratios of 13.9 and 0.03, respectively (see Table 1).
  • Cu-complex molecules remain intact within the as-prepared SSZ-13 crystals (see Cu-SSZ13-1 in Figure 2 ) and SEM images reveal an average crystal size of 4-7 ⁇ m (see Cu-SSZ13-1 in Figure 3 ).
  • the Cu-containing SSZ-13 was calcined at 550°C in air in order to remove the organic moieties precluded inside of the microporous material during the crystallization process.
  • the gel was transferred to an autoclave with a Teflon liner and heated to a temperature of 150°C during 14 days under static conditions.
  • the sample after hydrothermal crystallization was filtered and washed with abundant distilled water, and finally dried at 100°C.
  • the solid was characterized by Powder X-ray Diffraction (PXRD) obtaining the characteristic PXRD pattern of the SSZ-13 material (see Cu-SSZ13-2 in Figure 1 ).
  • the chemical analysis of the resultant solid indicates a Si/Al and Cu/(Si+Al) ratios of 14.2 and 0.06, respectively (see Table 1).
  • Cu-complex molecules remain intact within the as-prepared SSZ-13 crystals (see Cu-SSZ13-2 in Figure 2 ) and SEM images reveal an average crystal size of 4-7 ⁇ m (see Cu-SSZ13-2 in Figure 3 ).
  • the Cu-containing SSZ-13 was calcined at 550°C in air in order to remove the organic moieties precluded inside of the microporous material during the crystallization process.
  • a 20%wt aqueous solution of copper (II) sulfate (98%wt, Alfa) was mixed with 33 mg of tetraethylenepentamine (TEPA, 99%wt, Aldrich) and kept under stirring during 2 hours.
  • TEPA tetraethylenepentamine
  • 951 mg of an aqueous solution of N,N,N-trimethyl-1-adamantammonium hydroxide (TMaDA, 16%wt) and 143 mg of an aqueous solution of sodium hydroxide (20%wt) were added and maintained under stirring during 15 minutes.
  • the gel was transferred to an autoclave with a Teflon liner and heated to a temperature of 150°C during 14 days under static conditions.
  • the sample after hydrothermal crystallization was filtered and washed with abundant distilled water and finally dried at 100°C.
  • the solid was characterized by Powder X-ray Diffraction (PXRD) obtaining the characteristic PXRD pattern of the SSZ-13 material (see Cu-SSZ13-3 in Figure 1 ).
  • the chemical analysis of the resultant solid indicates a Si/Al and Cu/(Si+Al) ratios of 10.6 and 0.06, respectively (see Table 1).
  • the Cu-containing SSZ-13 was calcined at 550°C in air in order to remove the organic moieties precluded inside of the microporous material during the crystallization process.
  • the gel was transferred to an autoclave with a Teflon liner and heated to a temperature of 150°C during 14 days under static conditions.
  • the sample after hydrothermal crystallization was filtered and washed with abundant distilled water and finally dried at 100°C.
  • the solid was characterized by Powder X-ray Diffraction (PXRD) obtaining the characteristic PXRD pattern of the SSZ-13 material (see Cu-SSZ13-4 in Figure 1 ).
  • the chemical analysis of the resultant solid indicates a Si/Al and Cu/(Si+Al) ratios of 11.2 and 0.08, respectively (see Table 1).
  • Cu-complex molecules remain intact within the as-prepared SSZ-13 crystals (see Cu-SSZ13-4 in Figure 2 ) and SEM images reveal an average crystal size of 4-7 ⁇ m (see Cu-SSZ13-4 in Figure 3 ).
  • the Cu-containing SSZ-13 was calcined at 550°C in air in order to remove the organic moieties precluded inside of the microporous material during the crystallization process.
  • the gel was transferred to an autoclave with a Teflon liner, and heated to a temperature of 150°C during 12 days under static conditions.
  • the sample after hydrothermal crystallization was filtered and washed with abundant distilled water and finally dried at 100°C.
  • the solid was characterized by Powder X-ray Diffraction (PXRD) obtaining the characteristic PXRD pattern of the SSZ-13 material (see Cu-SSZ13-5 in Figure 4 ).
  • PXRD Powder X-ray Diffraction
  • the Cu-containing SSZ-13 was calcined at 550°C in air in order to remove the organic moieties precluded inside of the microporous material during the crystallization process.
  • a 20%wt aqueous solution of copper (II) sulfate (98%wt, Alfa) was mixed with 11 mg of triethylenetetramine (TETA, 99%wt, Aldrich) and kept under stirring during 2 hours.
  • TETA triethylenetetramine
  • 246 mg of an aqueous solution of N,N,N-trimethyl-1-adamantammonium hydroxide (TMaDA, 14.4%wt) 60.8 mg of an aqueous solution of sodium hydroxide (20%wt) were added and maintained under stirring during 15 minutes.
  • TMaDA N,N,N-trimethyl-1-adamantammonium hydroxide
  • the gel was transferred to an autoclave with a Teflon liner, and heated to a temperature of 150°C during 12 days under static conditions.
  • the sample after hydrothermal crystallization was filtered and washed with abundant distilled water and finally dried at 100°C.
  • the solid was characterized by Powder X-ray Diffraction (PXRD) obtaining the characteristic PXRD pattern of the SSZ-13 material (see Cu-SSZ13-6 in Figure 4 ).
  • PXRD Powder X-ray Diffraction
  • the Cu-containing SSZ-13 was calcined at 550°C in air in order to remove the organic moieties precluded inside of the microporous material during the crystallization process.
  • a 20%wt aqueous solution of copper (II) sulfate (98%wt, Alfa) was mixed with 47 mg of tetraethylenepentamine (TEPA, 99%wt, Aldrich), and kept under stirring during 2 hours.
  • TEPA tetraethylenepentamine
  • 1335 mg of an aqueous solution of N,N,N-trimethyl-1-adamantammonium hydroxide (TMaDA, 16%wt) was added and maintained under stirring during 15 minutes.
  • 16 mg of aluminum hydroxide (66%wt, Sigma-Aldrich) and 740 mg of colloidal silica (Ludox AS40, 40%wt, Aldrich) were introduced in the synthesis mixture and maintained under stirring.
  • the gel was transferred to an autoclave with a Teflon liner and heated to a temperature of 150°C during 14 days under static conditions.
  • the sample after hydrothermal crystallization was filtered and washed with abundant distilled water and finally dried at 100°C.
  • the solid was characterized by Powder X-ray Diffraction (PXRD), obtaining the characteristic PXRD pattern of the SSZ-13 material (see Cu-SSZ13-7 in Figure 4 ).
  • the chemical analysis of the resultant solid indicates a Si/Al and Cu/(Si+Al) ratios of 23.7 and 0.01, respectively (see Table 1).
  • the Cu-containing SSZ-13 was calcined at 550°C in air in order to remove the organic moieties precluded inside of the microporous material during the crystallization process.
  • the gel was transferred to an autoclave with a Teflon liner and heated to a temperature of 150°C during 14 days under static conditions.
  • the sample after hydrothermal crystallization was filtered and washed with abundant distilled water and finally dried at 100°C.
  • the solid was characterized by Powder X-ray Diffraction (PXRD) obtaining the characteristic PXRD pattern of the SSZ-13 material (see Cu-SSZ13-8 in Figure 4 ).
  • the chemical analysis of the resultant solid indicates a Si/Al and Cu/(Si+Al) ratios of 13.1 and 0.02, respectively (see Table 1).
  • the Cu-containing SSZ-13 was calcined at 550°C in air in order to remove the organic moieties precluded inside of the microporous material during the crystallization process.
  • Example 10 Catalytic tests on SCR of NOx over different Cu-SSZ13 synthesized by the present invention.
  • the activity of the samples for the catalytic reduction of NOx was studied in a fixed bed, quartz tubular reactor of 2.2 cm of diameter and 53 cm of length.
  • the catalyst was prepared with a particle size of 0.25-0.42 mm. It was introduced in the reactor, heated up to 550°C (see reaction conditions in Table 2) and maintained at these temperatures for one hour under nitrogen flow. After that the desired reaction temperature was set and the reaction feed admitted.
  • the SCR of NOx was studied using NH 3 as reductor.
  • the NOx present in the outlet gases from the reactor were analyzed continuously by means of a chemiluminiscence detector (Thermo 62C).
  • the catalytic results are summarized in Table 3.
  • Table 1 Chemical analyses of Cu-SSZ-13 materials synthesized in the present invention Sample Si/Al Cu/(Si+Al) Cu-SSZ13-1 13.9 0.03 Cu-SSZ13-2 14.2 0.06 Cu-SSZ13-3 10.6 0.06 Cu-SSZ13-4 11.2 0.08 Cu-SSZ13-7 23.7 0.01 Cu-SSZ13-8 13.1 0.02 Table 2: Reaction conditions for SCR of NOx.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
EP13801583.9A 2012-12-12 2013-12-06 One-pot method for the synthesis of cu-ssz-13 Active EP2931406B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL13801583T PL2931406T3 (pl) 2012-12-12 2013-12-06 Sposób syntezy cu-ssz-13 w jednym naczyniu reakcyjnym

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA201200784 2012-12-12
PCT/EP2013/075785 WO2014090698A1 (en) 2012-12-12 2013-12-06 One-pot method for the synthesis of cu-ssz-13, the compound obtained by the method and use thereof

Publications (2)

Publication Number Publication Date
EP2931406A1 EP2931406A1 (en) 2015-10-21
EP2931406B1 true EP2931406B1 (en) 2019-05-22

Family

ID=49724594

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13801583.9A Active EP2931406B1 (en) 2012-12-12 2013-12-06 One-pot method for the synthesis of cu-ssz-13

Country Status (14)

Country Link
US (1) US9878313B2 (enrdf_load_stackoverflow)
EP (1) EP2931406B1 (enrdf_load_stackoverflow)
JP (1) JP6239001B2 (enrdf_load_stackoverflow)
KR (1) KR20150093664A (enrdf_load_stackoverflow)
CN (1) CN104812469B (enrdf_load_stackoverflow)
BR (1) BR112015013822A2 (enrdf_load_stackoverflow)
CA (1) CA2887542A1 (enrdf_load_stackoverflow)
CL (1) CL2015001570A1 (enrdf_load_stackoverflow)
ES (1) ES2739650T3 (enrdf_load_stackoverflow)
IN (1) IN2015DN02842A (enrdf_load_stackoverflow)
PL (1) PL2931406T3 (enrdf_load_stackoverflow)
RU (1) RU2643969C2 (enrdf_load_stackoverflow)
WO (1) WO2014090698A1 (enrdf_load_stackoverflow)
ZA (1) ZA201503125B (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110407221A (zh) * 2019-06-21 2019-11-05 合肥派森新材料技术有限公司 一种菱沸石分子筛的制备方法、scr催化剂的制备方法
CN112279266A (zh) * 2020-12-29 2021-01-29 中化学科学技术研究有限公司 一种Cu-SSZ-13@SSZ-13核壳型分子筛及其制备方法和应用
WO2023180462A1 (en) 2022-03-23 2023-09-28 Umicore Ag & Co. Kg Scr zeolite catalysts for reduced n2o formation
WO2023180460A1 (en) 2022-03-23 2023-09-28 Umicore Ag & Co. Kg Copper and manganese containing chabazite scr catalyst for n2o reduction
WO2023180461A1 (en) 2022-03-23 2023-09-28 Umicore Ag & Co. Kg Scr zeolite catalysts for improved nox reduction

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX348176B (es) * 2012-09-05 2017-06-02 Lumenco Llc Trazado, configuracion y formacion de imagen de pixel para matrices de micro-lentes de base redonda o cuadrada para lograr un movimiento tridimensional y multi-direccional de volumen completo.
RU2703462C1 (ru) * 2013-12-02 2019-10-17 Джонсон Мэтти Паблик Лимитед Компани СМЕШАННЫЙ ТЕМПЛАТНЫЙ СИНТЕЗ Cu-CHA С ВЫСОКИМ СОДЕРЖАНИЕМ ДИОКСИДА КРЕМНИЯ.
CN104386706B (zh) * 2014-11-04 2016-07-06 南开大学 以锌胺络合物为模板剂合成cha型分子筛的方法
ES2589059B1 (es) * 2015-05-05 2017-08-17 Consejo Superior De Investigaciones Cientificas SÍNTESIS DIRECTA DE Cu-CHA MEDIANTE LA COMBINACIÓN DE UN COMPLEJO DE Cu Y TETRAETILAMONIO, Y APLICACIONES EN CATÁLISIS
CN105251528A (zh) * 2015-09-14 2016-01-20 天津大学 以四乙基氢氧化铵与铜氨络合物混合作为模板剂一步合成Cu-CHA催化剂的方法
CN108136380B (zh) * 2015-10-12 2021-07-30 优美科股份公司及两合公司 含铜小孔沸石的一锅合成
CN106622356B (zh) * 2015-11-03 2019-03-05 中触媒新材料股份有限公司 一种铜改性分子筛选择性还原催化剂及其制备方法和应用
CN106179472A (zh) * 2015-12-10 2016-12-07 华中科技大学 一种Cu-SSZ-13分子筛催化剂的制备方法及其用途
CN109071245B (zh) * 2016-02-01 2022-03-04 优美科股份公司及两合公司 用于直接合成含铁的aei-沸石催化剂的方法
EP3463652A1 (en) * 2016-05-24 2019-04-10 ExxonMobil Chemical Patents Inc. A synthetic zeolite comprising a catalytic metal
CN106238092A (zh) * 2016-07-13 2016-12-21 无锡威孚环保催化剂有限公司 一步法合成Cu‑SSZ‑13分子筛催化剂的方法
CN107961813B (zh) * 2016-10-19 2020-07-28 中国科学院大连化学物理研究所 提高柴油车尾气脱硝分子筛整体催化剂涂层均匀度的方法
EP3533762A4 (en) * 2016-10-25 2019-11-20 JGC Catalysts and Chemicals Ltd. ZEOLITE OF CHABAZITE TYPE FOR SUBSTRATE COATING
EP3323785A1 (en) * 2016-11-18 2018-05-23 Umicore AG & Co. KG Crystalline zeolites with eri/cha intergrowth framework type
CN109110780A (zh) * 2017-06-22 2019-01-01 中国科学院宁波材料技术与工程研究所 一种原位水热合成Cu-SSZ-13分子筛的方法
FR3069238B1 (fr) 2017-07-18 2019-07-12 IFP Energies Nouvelles Synthese directe d'un materiau aluminosilicate microporeux de structure afx comprenant du cuivre et utilisation de ce materiau
CN107597190B (zh) * 2017-08-14 2019-12-06 湖北大学 一种沸石分子筛晶粒表面组装金属有机骨架膜的制备方法及其应用
ES2703222A1 (es) 2017-09-07 2019-03-07 Haldor Topsoe As Catalizador que comprende un nuevo tamiz molecular que pertenece a la familia ERI y uso del catalizador
ES2703220A1 (es) 2017-09-07 2019-03-07 Haldor Topsoe As Método para la preparación de un nuevo tamiz molecular de ERI
ES2703221A1 (es) 2017-09-07 2019-03-07 Haldor Topsoe As Nuevo tamiz molecular de ERI y un método para su preparación
CN108160105B (zh) * 2017-12-12 2020-10-27 南开大学 用于甲烷选择性催化还原分子筛催化剂及其合成方法
CN109985663B (zh) * 2017-12-29 2020-09-08 华中科技大学 一种对一锅法原位合成的Cu-SSZ-13分子筛进行后处理的方法
CN108190907B (zh) * 2018-02-06 2021-02-19 四川润和催化新材料股份有限公司 一种ssz-13分子筛及其制备方法
EP3793727B1 (en) 2018-05-14 2022-06-22 UMICORE AG & Co. KG Stable small-pore zeolites
WO2020039074A1 (en) 2018-08-24 2020-02-27 Umicore Ag & Co. Kg Method for the preparation of a molecular sieve of the cha-type
CN112912340B (zh) * 2018-10-29 2024-01-02 太平洋工业发展公司 高酸度和低二氧化硅与氧化铝比率(sar)的ssz-13沸石的制备方法
US11278875B2 (en) 2018-12-20 2022-03-22 Ecovyst, Inc Direct synthesis of metal-containing CHA zeolites
US10703986B1 (en) 2019-01-30 2020-07-07 Exxonmobil Research And Engineering Company Selective oxidation using encapsulated catalytic metal
CN110683559A (zh) * 2019-08-22 2020-01-14 上海工程技术大学 一种超薄ssz-13分子筛膜的绿色合成方法
CN110876957B (zh) * 2019-10-31 2021-01-22 山东国瓷功能材料股份有限公司 分子筛Cu-SSZ-13、其合成方法、催化剂和用途
CN111704145A (zh) * 2020-06-05 2020-09-25 浙江天地环保科技股份有限公司 一种原位合成纳米氢型Cu-SSZ-13分子筛的方法
CN112028086B (zh) * 2020-08-25 2022-07-12 华中科技大学 一种纳米Cu-SSZ-13分子筛及其一步合成方法与应用
KR20220060315A (ko) * 2020-11-04 2022-05-11 현대자동차주식회사 Scr 촉매의 제조 방법 및 이에 의하여 제조된 scr 촉매
CN112279269B (zh) * 2020-11-05 2021-07-02 天津派森新材料技术有限责任公司 一步法制备Cu-SSZ-39分子筛的方法
CN112675900A (zh) * 2020-12-24 2021-04-20 江南大学 一种抗水硫中毒、抗水热老化的scr催化剂及其制备方法
EP4019127A1 (en) * 2020-12-28 2022-06-29 Basf Corporation Flouride-containing small-pore zeolite compositions
CN115196651B (zh) * 2021-04-12 2024-03-19 中国科学院大连化学物理研究所 一种无钠Cu-SSZ-13沸石的制备方法及其应用
CN117715866A (zh) * 2021-07-30 2024-03-15 庄信万丰股份有限公司 合成低sar菱沸石型沸石的方法和由此获得的沸石
CN114655963B (zh) * 2022-03-31 2022-12-20 山东泓泰恒瑞新材料有限公司 一种ssz-13分子筛复合材料的制备方法
CN115779958B (zh) * 2022-11-28 2024-03-22 陕西煤业化工技术研究院有限责任公司 一种SSZ-13分子筛负载Cu0催化剂及其制备方法和应用

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4544538A (en) * 1982-07-09 1985-10-01 Chevron Research Company Zeolite SSZ-13 and its method of preparation
US5591421A (en) 1994-07-11 1997-01-07 Chevron U.S.A. Inc. Zeolite SSZ-41
FR2869894B1 (fr) * 2004-05-10 2007-02-23 Inst Francais Du Petrole Methode de synthese de metalloaluminosilicate cristallise par synthese directe
CA2664214C (en) * 2006-09-25 2014-11-04 Chevron U.S.A. Inc. Preparation of molecular sieves using a structure directing agent and an n,n,n-triakyl benzyl quaternary ammonium cation
US20080159950A1 (en) * 2006-12-27 2008-07-03 Miller Stephen J Preparation of molecular sieve ssz-13
US7998423B2 (en) * 2007-02-27 2011-08-16 Basf Corporation SCR on low thermal mass filter substrates
MY151931A (en) * 2007-02-27 2014-07-31 Basf Catalysts Llc Bifunctional cataysts for selective ammonia oxidation
BRPI0808091A2 (pt) * 2007-02-27 2014-07-15 Basf Catalysts Llc Catalisador, sistema de tratamento de gás de exaustão, processo para a redução de óxidos de nitrogênio, e, artigo de catalisador.
EP3778484A1 (en) * 2008-05-21 2021-02-17 Basf Se Process for the direct synthesis of cu containing zeolites having cha structure
CN102614908A (zh) * 2012-03-16 2012-08-01 北京工业大学 用于氨选择性催化消除NOx的SSZ-13负载Cu-Fe催化剂的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110407221A (zh) * 2019-06-21 2019-11-05 合肥派森新材料技术有限公司 一种菱沸石分子筛的制备方法、scr催化剂的制备方法
CN112279266A (zh) * 2020-12-29 2021-01-29 中化学科学技术研究有限公司 一种Cu-SSZ-13@SSZ-13核壳型分子筛及其制备方法和应用
CN112279266B (zh) * 2020-12-29 2021-04-06 中化学科学技术研究有限公司 一种Cu-SSZ-13@SSZ-13核壳型分子筛及其制备方法和应用
WO2023180462A1 (en) 2022-03-23 2023-09-28 Umicore Ag & Co. Kg Scr zeolite catalysts for reduced n2o formation
WO2023180460A1 (en) 2022-03-23 2023-09-28 Umicore Ag & Co. Kg Copper and manganese containing chabazite scr catalyst for n2o reduction
WO2023180461A1 (en) 2022-03-23 2023-09-28 Umicore Ag & Co. Kg Scr zeolite catalysts for improved nox reduction

Also Published As

Publication number Publication date
CL2015001570A1 (es) 2015-10-09
WO2014090698A1 (en) 2014-06-19
JP2016506353A (ja) 2016-03-03
IN2015DN02842A (enrdf_load_stackoverflow) 2015-09-11
EP2931406A1 (en) 2015-10-21
BR112015013822A2 (pt) 2017-07-11
RU2643969C2 (ru) 2018-02-06
CA2887542A1 (en) 2014-06-19
KR20150093664A (ko) 2015-08-18
ES2739650T3 (es) 2020-02-03
RU2015127895A (ru) 2017-01-18
US9878313B2 (en) 2018-01-30
JP6239001B2 (ja) 2017-11-29
US20160271596A1 (en) 2016-09-22
PL2931406T3 (pl) 2020-03-31
CN104812469B (zh) 2017-05-03
ZA201503125B (en) 2019-09-25
CN104812469A (zh) 2015-07-29

Similar Documents

Publication Publication Date Title
EP2931406B1 (en) One-pot method for the synthesis of cu-ssz-13
US10792617B2 (en) Method for the direct synthesis of Cu-containing silicoaluminate material with the AEI zeolite structure, and the catalytic applications thereof
US10526208B2 (en) Method for preparing the silicoaluminate form of the AEI zeolite structure with high yields, and its application in catalysis
US10676367B2 (en) Direct synthesis of Cu-CHA by means of combining a Cu complex and tetraethylammonium and applications in catalysis
RU2602085C2 (ru) Способ прямого синтеза cu-sapo-34
JP2004509044A (ja) 大きい及び特大の細孔のホウケイ酸塩ゼオライトにおけるヘテロ原子格子置換方法
EP3153471A1 (en) Synthesis of sapo-18 and the catalytic applications thereof
Wang et al. Fluoride-free synthesis of high-silica RHO zeolite for the highly selective synthesis of methylamine
Corma et al. Method for preparing the silicoaluminate form of the aei zeolite structure with high yields, and its application in catalysis
Corma et al. Synthesis of zeolite with the cha crystal structure, synthesis process and use thereof for catalytic applications

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150512

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UMICORE AG & CO. KG

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20181221

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013055827

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1135418

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190615

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190522

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190822

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190922

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190823

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190822

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1135418

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190522

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20191210

Year of fee payment: 7

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2739650

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200203

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013055827

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20191209

Year of fee payment: 7

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

26N No opposition filed

Effective date: 20200225

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20200102

Year of fee payment: 7

Ref country code: GB

Payment date: 20191206

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20191231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191206

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20201112

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190522

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20131206

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201207

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201206

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: MK

Payment date: 20221026

Year of fee payment: 10

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230602

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231010

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20231009

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602013055827

Country of ref document: DE